Hair preparations containing a diamide and process of use thereof



- Patented Sept. 15, 1964 3,149,338 HAIR iREPARATEflNS QGNTAHQTNG ADEAD/HER AND PRG-CESS 43F USE TE EREQF Loin Habicht, Aumuhle, nearHamburg, and Arno Kluge,

Bad Sorlen, Taunus, Germany, assignors to Qolgate- Palmolive Company,New York, N.Y., a corporation of Delaware No Drawing. Filed lune 17,1960, Ser. No. 36,754 (Ilaims priority, application Germany, duly 7,1959, P 23,1tl2 11 Claims. (Cl. l6787) The present invention relates toa cosmetic composition suitable for daily use in the care of the hair.More particularly it relates to hair cleansing and grooming compositionssuch as hair lotions, tonics, shampoos and the like which may be used inthe daily toilet.

in accordance with the present invention a cosmetic composition suitablefor daily use in the care of the hair and scalp comprises asubstantially non-volatile organic toilet agent for the daily care ofthe hair and a diamide compound having the formula wherein X is selectedfrom the group consisting of oxygen sulfur, R R R and R are selectedfrom the group consisting of hydrogen alkyl, alkylol and acyl, and R isselected from the group consisting of hydrogen and alkyl, said R R R Rand R containing up to two carbon atoms each, and from 40 to 99.45% of avolatile aqueous solvent medium, said composition having a pH of from 4to and being free of reducing agents. Suitable such compounds includebiuret, thiobiuret, dithiobiuret, and their waterand alcohol-solublemonoand polyalkyl, -alkylol and -acyl derivatives wherein the alkyl,alkylol and acyl groups have in general not more than 2 carbon atoms,e.g. l-rnethyl-biuret, S-methylbiuret, l-ethyl-biuret,1,5-dimethyl-biuret, 1,3,5-trimethylbiuret, l-hydroxymethyl-biuret,1,5-dihydroxymethyl-biuret, I-acetyl-biuret, 1-forrnyl5-acetyl-biuret,1,5-dimethyl-l-acetyl-biuret, 1,3,5-trimethyl-l-acetyl-biuret,3-ethyll-acetyl-biuret, l-methyl-thiobiuret, l-ethyl-thiobiuret, 1acetyl-thiobiuret, 1 hydroxymethyl-thiobiuret, andl-methyl-dithiobiuret.

The cosmetic compositions of the present invention may be prepared in awide variety of physical forms. They may be liquids, pastes or solidsand may consist of one or more phases. They may, for example, constitutea single aqueous or aqueous-alcoholic phase, or may comprise an aqueousand a separate oily phase as in two layer systems or emulsions of thewater-in-oil or oil-inwater types.

The instant compositions and their constituents are skin-compatible,being suitable for periodic use at short, i.e. daily or at the mostweekly, intervals, as distinguished from decorative or treatingcompositions such as hair dye ing or waving compositions which can beused only at much greater intervals. Thus it is contemplated that thepresent cosmetic compositions may be prepared in the form of daily hairgrooming products such as hair 10- tions, hair dressings, hair tonicsand the like, or they may be prepared in the form of hair cleansingproducts such as shampoos, the non-volatile organic toilet agent fordaily care of the hair being present in each instance in an amount from0.5 to 98% by Weight of the composition.

In the case of hair grooming compositions, the nonvolatile organictoilet agent for the daily care of the hair stituent containing 8 to 26carbon atoms.

is an agent which facilitates grooming of the hair and helps to keep thehair in place. Such hair groonnng agents include, e.g., castor oil,mineral o1l, lower alkoxypolyoxy lower alkylene glycols such asbutoxypolyoxypropylene glycol, higher molecular weight copolymers ofrandom mixtures of ethylene oxide and propylene oxide, esters of fattyacids such as isopropylmyristate or the coconut oil fatty acid ester ofpolyethylene glycol having an average molecular Weight of about 400,polyhydric alcohols such as glycerol and propylene glycol, gums such asgum tragacanth, lacquers such as shellac, and the like. It is preferredto employ those substantially non-volatile organic hair grooming agentswhich have a molecular weight greater than about and preferably greaterthan about 200 and which contain an alcoholic hydroxyl group such as theaforementioned glycols, polyhydric alcohols, polymerized alkyleneoxides, and castor oil. The foregoing organic hair grooming materialsdesirably are employed in the instant hair grooming preparations in anamount from 0.5 to 50% and higher depending on the nature of therespective compound and its compatibility in the desired system.

In the case of hair cleansing compositions or shampoos, the non-volatileorganic toilet agent for the daily care of the hair is a cleansing agentsuch as a water-soluble organic detergent. Preferably this detergent isan anionic sulfate or sulfonate, i.e. a sulfated or sulfonated compoundhaving a hydrophobic substituent containing 8 to 26 carbon atoms,desirably from 12 to 18 carbon atoms, per molecule.

Detergents of this preferred type which may be suitably employed includethe sulfuric acid esters of polyhydric alcohols incompletely esterifiedwith higher fatty acids, e.g., coconut oil monoglyceride monosulfate andfallow diglyceride monosulfate; the long chain'pure or mixed'allrylsulfates such as lauryl sulfate, cetyl sulfate, and higher fatty alcoholsulfates derived from coconut oil; the hydroxy sulfonated higher fattyacid esters such as, e.g., higher fatty acid esters of2,3-dihydroxypropane sulfonic acid; the lugher fatty acid esters of lowmolecular weight alkyiolsulfonic acids, e.g., oleic acid ester ofisethionic acid; the sulfated higher fatty acid alkylolamides such as,e.g., CthSIiOIZLrldC sulfates; the higher fatty acid amides of aminoalkyl sulfonic acids, e.g., the lauric amide of taurine, and the like.

Other anionic synthetic detergents which may be employed in shampoos arethe sulfonic acid salts of alkylated aromatic hydrocarbon compoundshaving an alkyl sub The aromatic portion of the molecule may be monoorpolynuclear, e.g., benzene, toluene, Xylene, naphthalene, phenanthrene,anthracene, etc., and may contain other substituents such as hydroxylgroups or short chain alkyl groups such as, e.g., in phenol, cresol,phenol ethers, toluene, Xylene, etc. The long chain alkyl substituent ofthe alkylated aromatic molecule preferably is saturated and may bestraight chain or branched. Representative long chain alkyl groupsinclude the dodecyl, hexyl, octyl, nonyl, and decyl groups as well asmixed alkyls derived from fatty materials, cracked parafiins or polymersof lower mono olefins, etc. In general, the alkylated aromaticdetergents employed will be a mixture of compounds having alkylsubstituents of varying chain length since the chain length is dependentupon the sharpness of the fractionation of the aliphatic hydrocarbonused for the alkylation. The average chain length of the alkylsubstituents shouldbe in general from 9 to 15 carbon atoms andpreferably between 12 and 14 carbon atoms.

These various anionic detergents are employed in shampoos prepared inaccordance with the present invention in the form of their water-solublesalts. Thus, detergents may be used in the form of their alkali salts,e.g.,

as sodium, potassium or lithium salts, or as ammonium salts, as well asin the form of salts of nitrogen containing bases, e.g., as salts of lowmolecular alkylolamines such as mono-, diand triethanolamine, and asmixtures of various of these salts.

Other anionic detergents which may also be employed includewater-soluble alkyl phosphates, sulfated ethylene oxide condensates ofhydrophobic materials such as higher fatty acids, fatty alcohols, alkylaromatic hydrocarbons and the like, sulfonated oils, soaps such assodium, potassium and triethanolamine soaps of higher fatty acidscontaining from 12 to 18 carbon atoms as well as mixtures of soaps beingespecially useful such as sodium laurate, sodium palmitate, sodiumoleate and the potassium and/or triethanolamine soaps of coconut oil,palm oil, and tallow fatty acids.

lauroyl pyridinium bromide, cetyl trimethyl ammonium chloride or cetylpyridinium chloride may also be used alone or'in combination with othercompatible detergents. Suitable salts of cationic detergents are thechloride, bromide, acetate and sulfate. V

Suitable detergents are furthermore the amphoteric detergents such assalts of the N-alkyl compounds of betaamino propionic acid wherein thealkyl group is derived from a fatty acid fatty acids.

Shampoos in accordance with the present invention may be prepared in anyconvenient physical form and may consist of one or more phases. Thussuch a shampoo such as the mixture of coconut oil 'may be a solidproduct such as a bar or a powder, or a clear, homogeneous single phaseliquid such as an aqueous or aqueous-alcoholic composition, or it maycontain two or more liquid or mixed liquid and solid phases, as in ablycomprise 'at least and prferably from to 40% "of the instant shampooswhen they are prepared in a liquid or paste formQand from 15 to 98% whenthe shampoo is prepared in the form of a solid'composition;

The diamide compounds of the present invention constitute a minorproportion, on the order of 0.05 to 10% of the instant hairpreparations, the most suitable amount depending on the characteristicsdesired; Thus, in a clear, homogeneous, single phase,.aqueous type ofhair preparation preferably an amount on the order of 0.25 to 'the caseof cream-shampoos, lotion-shampoos, pasteshampoos, and the like. Theforegoing detergents desir- 1.0% of the composition in employed. In asingle phase 1 For example, an'aqueous cosmetic composition may comprisefrom 0.05 to 10% of diamide, from 0.5 to 50% of the non-volatile organictoilet agent, and as the balance,

e. g.14099.45%, a volatile aqueous solvent medium such as water ormixtures of water and a lower monohydric alcohol such as ethanol orisopropyl alcohol. In the reparation of a clear, homogeneous singlephase aqueous shampoo, preferably 0.5 to 2% of one of the instantdiamide compounds, 5 to 20% water soluble detergent, and 7894.5% waterand other components are used, Whereas in a shampoo containing aqueousalcohol wherein said diamide compounds and detergents are each moresoluble, more than 2% of the diamide may be used in combination with 5to 40% of the detergent, the balance being aqueous alcohol and othercomponents. In solid, powder or cream shampoos amounts of 0.05 up to 10%of diamide are possible in combination with 15 to 98% of the detergentand'a balance of water and/ or other components.

The instant hair preparations may also contain as adjuvant materialsvarious substances such as vitamins, hormones, cholesterol, lanolin,bactericides, plant extracts, buffers, and the like in compatibleproportions, although the preparations should be free of substantialquantities of water insoluble sohd substanceswhich may be deposited onand clog the pores of the scalp. Desirably the present compositions havea pH of 4 to 10 as they appear to be most effective in this range.

The hair preparations of the invention exhibit unusua ly excellent hairgrooming properties. They render the hair soft and manageable, impart ahigh gloss and luster, and are particularly effective in controlling orpreventing the formation of dry flaky scales of sloughed-oif skin.

The efiiciency of aqueous compositions prepared in accordance with thepresent invention is favorably infiuenced by the presence of a watersoluble material which reduces the surfaceand/or interfacialatension ofwater (e.g. alcohol in alcoholic hair tonics, soaps or syntheticdetergents in shampoos, emulsifiers in hair dressings). The presence ofthese surface active materials is believed to reduce the interfacialtension between the aqueous phase containing the instant water solublediamides and the hair v and scalp so that soil and oily secretions aremore easily temperature or elevated temperature in the amount of water,alcohol or aqueous alcohol required for the respective hair preparation.Thereafter, the toilet agent for the daily care of the hair may be addedin the usual way, i.e.

in the case of hair tonics, liquid shampoos or hair rinses the hairgrooming agent may be added to the liquid containing the diamide of theinvention, and in the case of hair creams of the oil-in-water orwater-in-oil type, the

liquid containing the diamide may be heated to 50-70 C. and emulsifiedwith the molten fats, mineral oils orlike hair grooming agents, theemulsion, if necessary, being homogenized thereafter.

Cream shampoos formulated in accordance with the present invention maybe prepared by mixing an aqueous detergent paste with an appropriatediamide compound and any other desired components with stirring at anelevated temperature (4060 C.)..

Powder shampoos may be made by homogeneously mixing the desiredcomponents in a mixer.

. Specific hair preparations according to the invention are illustratedby the following examples. All parts indicated 'areby weight unlessotherwise specified.

EXAMPLE 1 v V Hair Lotion To 56 parts of ethyl alcohol 96% and 6 pmts ofglycerine 98%- ina suitable mixer 2 parts of biuret are added withstirring. After complete dissolutionof the biuret,

0.19 partof perfume and 0.01 part of dyestuif are introduced as coloringfor the lotion, and after short stirring 35.8 parts of deionizedwaterare added. For clarification 0.1 part of magnesium carbonateisstirred into the solution and filtered oif again.

Water 45 .6

The hair lotions of Examples 2 and 3 are prepared in a Way analogous toExample 1.

EXAMPLE 4 Hair Cream [Oil-imwzxter emulsion] 14 parts of diglycollaurate, 34 parts of mineral oil and 0.2 part of a preservative (e.g.methyl-p-hydroxy benzoic acid ester) are heated to 80 C. This mix isslowly and thoroughly stirred into a solution of 1 part of thiobiuret in50.5 parts of water. After cooling to 35 C., 0.3 part of perfume isadded. Finally the cream is homogenized on a roller mill.

EXAMPLE 5 Hair Cream [Oil-in-water emulsion] Part I Parts Mineral oil33.0

Beeswax 3.0 Stearic acid 0.5 Cetyl alcohol 1.3 Preservative 0.2

Part II Borax 0.25

Triethanolarnine 1.85 1,5-dihydroxymethyl-biuret 5.00 Water 54.60

Part III Perfume 0.30

Part I is heated to 6065 C. and slowly added with vigorous stirring topart 11 previously heated to 60-65 C. The cream is cooled with stirringto 35 C. at which temperature part III is added.

EXAMPLE 6 Hair Cream [Water-in-oil emulsion] Part I Parts Bees wax n 1.5Oleic acid 1.0 Mineral oil 40.6 Preservative 0.2

Part II Milk of lime 0.14% 50.0 l-formyl-S-acetyl-biuret 1 .0

Part III Magnesium sulfate solution 10% 5.0

Part IV Perfume 0.7

6 Part I is heated to 7075 C. Then part H previously heated to 60 C. isslowly added with thorough stirring, and finally part III is introduced.The cream is stirred at 70 C. for 10 minutes and then slowly cooled withstirring to 55 C. At this temperature, part IV is added. Then the creamis cooled to 35 C. and homogenized at 30 C.

EXAMPLE 7 Liquid Shampoo Part I Parts Oleic acid 5.0 Coconut oil fattyacid 4.0 Triethanolamine 5.5 Propylene glycol 5.0 Preservative 0.2

Part II Ethylene diamine tetraacetic acid sodium salt 0.5 Biuret 1.5

Water 78.0

Part III Perfume 0.3

Part I is heated to C. while stirring. After a homogeneous mix isobtained, part II previously heated to 35 C. is added with cautiousstirring and finally part III is introducedf EXAh/IPLE 8 Powder ShampooParts Sodium lauryl isethionate 60.0 Sodium bicarbonate 34.5l-methyl-biuret 5 .0 Perfume 0.5

The solid components are homogeneously mixed in a mixer and the perfumeis added by spraying it on the powder while moving the mass in themixer.

EXAMPLE 9 Liquid Shampoo 97.4 parts of an aqueous alcoholic solutioncontaining 20 parts of ammonium coconut oil monoglyceride monosulfateand 20 parts of ethyl alcohol are heated to -35 C. 2 parts of1,3,5-trimethylbiuret, 0.2 part of preservative, 0.05 part of dyestuffand 0.35 part of perfume are stirred successively into this solution.

EXAMPLE 10' Liquid Shampoo Parts N-lauryl-beta-amino-propionic acidtriethanolamine salt, 40% 50.0

Coconut oil fatty acid diethanolamide 2.0 1,5-dimethylbiuret 3.0Perfume, preservative, coloring 0.6 Water 44.4

This composition is prepared in a similar way as described in Example 9.

EXAMPLE 11 Cream Shampoo 91.8 parts of an aqueous sodium lauryl sulfatepaste containing about 45- parts of sodium lauryl sulfate are heated to5060 C. To this mix a melt from 2 parts of polyethyleneglycol-400-distearate, 1.5 parts of magnesium stearate and 1 part ofoleyl alcohol and then 0.2 par-t of a preservative and 3 parts ofthiobiuret. are added with stirring. After cooling to 40 C. 0.5 part ofperfume is introduced.

EXAMPLE 12 Hair Rinse 7 Parts Stearyl dimethyl benzyl ammonium chloride4.0 Polyglycol-400-distearate 3 .0

l-hydroxymethyl-biuret 2.0 Perfume, preservative 0.5

Water 90.5

From all components an aqueous solution is prepared at room temperature.After standingrfor 24 hours the solution is filtered.

Although the present invention has been described with reference toparticular embodiments and examples, it

wherein X is selected from the group consisting of oxygen and sulfur, RR R and R are selected from the group consisting of hydrogen, alkyl,alkylol and acyl, and R is selected from the group consisting ofhydrogen and alkyl, said R R R R and R containing up to two carbon atomseach, and from to 99.45% of a volatile aqueousj solvent medium, saidcomposition having a pH of from 4 to 10 and being freeof reducingagents.

2. A cosmetic composition as set forth in claim 1 wherein said diamideis biuret.

3. A shampoo composition comprising from about 5 to 98% of a watersoluble organic detergent, and .05 to 10% of a diamide compound havingthe formula wherein X is selected from the group consisting of oxygen 7and sulfur, R R R and R are selected from the group 7 consisting ofhydrogen, alkyl, alkylol and acyl, and R is selected from the groupconsisting of hydrogen and alkyl, said R R R R and R containing up totwo carbon atoms each, and water as the balance, said composition havinga pH of 4 to '10 and being free of reducing agents.

4. A shampoo composition as set forth in claim 3 wherein said diamide isbiuret.

5. A hair grooming composition suitable for daily use in the care of thehair'and scalp which comprises about 0.5 to by weight of a substantiallynon-volatile organic hair grooming agent containing an, alcoholichydroxyl group and having a molecular weight greater than about '75,0.05 to 10% of a dianiide compound having the'formula J said R R R R andR containing up to two carbon atoms each, and 40 to 99.45% of a volatileaqueous sol- .ventmedium, said comp ositionihaving a pH oft-4 to 10 andbeing free of reducing agents. 5

6. A hair grooming preparation as set forth in claim 5 wherein said hairgrooming agent is glycerine. V

7. A process for the treatment of the hair and scalp which comprises thedaily application thereto of a substantially non-volatile toilet agentfor the daily care of the hair and about 0.05 to 10% by weight of adiamide CO1 pound having the formula wherein X is selected from thegroup consisting of oxygen and sulfur, R R R and R are selected from thegroup consisting of hydrogen, alkyl, alkylol and aryl, and R is selectedfrom the group consisting of hydrogen and alkyl, said R R R R and Rcontaining up to two carbon atoms each, the said toilet agent anddiamide compound being applied to the hair and scalp at a pH of 4 .to10.

8. A cosmetic composition suitable for daily use in the care of the hairand scalp which comprises a substantially non-volatile toilet agent forthe daily care of the hair and from about 0.25 to 2.0% by weight of adiamide compound having the formula wherein X is selected from the groupconsisting of oxygen and sulfur, R R R and R are selected from the groupconsisting of hydrogen, alkyl, alkylol and acyl, and R is selected fromthe group consisting ofhydrogen and alkyl, said R R R R and R containingup to two carbon atoms each, said composition having a pH of 4 to 10when disposed in an aqueous liquid and being free of reducing agents. i

9. A cosmetic composition suitable. for daily use in the care of thehair and scalp which comprises a substantially non-volatile toilet agentfor the daily care of the hair and from about 0.25 to 1.0% by weight ofa diamide com pound having the formula wherein X is selected from thegroup consisting of oxygen and sulfur, R R R and R are selected from thegroup consisting of hydrogen, alkyl, alkylol and acyl, and R is selectedfrom the group consisting and hydrogen and 'alkyl, V

wherein X is selected from the group consisting of oxygen and sulfur, RR R and R are selected from the group consisting of hydrogen, alkyl,alkylol and acyl, and R is selected from the group consisting ofhydrogen and alkyl, said R R ,"R R and R containing up, to two carbonatoms each, said composition having a pH of 4 to 10 when disposed in anaqueous liquid and being free of reducing agents. V

11. A' hair groom ng composition suitable for daily use in the careofthe hair and scalp which comprises about;

9 10 0.5 to 50% by weight of mineral oil, 0.05 to 10% of 2. ReferencesCited in the file of this patent dialm'de compound having the formulaUNITED STATES PATENTS R1\ /R4 2,371,112 Sperry Mar. 6, 1945 2,371,113Sperry Mar. 6, 1945 OX E 0X 5 2,813,783 Gleim Nov. 19, 1957 FOREIGNPATENTS wherein X is selected from the group consisting of oxygen 75 320N th 1 d Jul 15 1954 and sulfur, R R R and R are selected from the group6 er an s n y consisting of hydrogen, alkyl, alkylol and acyl, and R is10 OTHER REFERENCES selected from the group consisting of hydrogen 311dy Kurzer: Chemical Reviews, vol. 56, pages 95 to 197, said R R R R and Rcontaining up to two carbon February-June 1956. atoms each, and 40 to99.45% of a volatile aqueous sol- Harry: Modern Cosmeticology, vol. 1,Fourth edition,

vent medium, said composition having a pH of 4 to 10. published byLeonard Hill Ltd., 1955, pages 432 to 434.

1. AN AQUEOUS COSMETIC COMPOSITION SUITALBE FOR DAILY USE IN THE CARE OFTHE HAIR AND SCALP WHICH COMPRISES ABOUT 0.5 TO 50% BY WEIGHT OF ASUBSTANTIALLY NON-VOLATILE ORGANIC TOILET AGENT FOR THE CARE OF THEHAIR, ABOUT 0.05 TO 10% OF A DIAMIDE COMPOUND HAVING THE FORMULA